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New copper(II) salicylaldimine derivatives for mild oxidation of cyclohexane

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Abstract

Two new salicylaldiminato-copper(II) complexes, [\(\hbox {Cu}(\mathbf{L}^{\mathbf{1}})_{2}\)] (1) and [\(\hbox {Cu}(\mathbf{L}^{\mathbf{2}})_{2}\)] (2) (where \(\mathbf{HL}^{\mathbf{1}}=4\)-tert-Butyl-2-[(thiophen-2-ylmethylimino)-methyl]-phenol and \(\mathbf{HL}^{2} = 2,4\)-Di-tert-butyl-6-[(thiophen-2-ylmethylimino)-methyl]-phenol), endowed with a pendant thiophenyl moiety, were synthesized and characterized using standard spectroscopic techniques (FT-IR, UV-Vis, MS) and elemental analysis. Complexes 1 and 2 were unequivocally characterized by single crystal X-ray crystallography, which confirmed bidentate bis-chelation of the deprotonated -\(\mathbf{L}^{\mathbf{1}}\) and -\(\mathbf{L}^{\mathbf{2}}\) ligands to the copper (II) centres via the phenoxo and imine atoms forming square planar complexes. The copper(II)-hydroperoxo derivatives of 1 and 2 ([\((\mathbf{L}^{\mathbf{1}})_{2}\hbox {Cu}^\mathrm{II}\hbox {-OOH}\)] (3) and [\((\mathbf{L}^{\mathbf{2}})_{2}\hbox {Cu}^\mathrm{II}\hbox {-OOH}\)] (4)) were also synthesized and the formation of the active intermediate in solution studied. Complexes 1 and 2 were tested as catalyst precursors in cyclohexane oxidation under mild reaction conditions using hydrogen peroxide (\(\hbox {H}_{2} \hbox {O}_{2}\)) as a terminal oxidant, and were found to catalyse oxidation of the substrate with yields comparable to similar mononuclear and even multinuclear copper complexes.

Graphical Abstract

 Synopsis Synthesis, characterisation, and molecular structure of salicylaldiminato-copper(II) complexes, and their catalytic evaluation in the oxidation of cyclohexane employing hydrogen peroxide as a terminal oxidant have been studied. The complexes catalysed conversion of cyclohexane with appreciable yields.

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Scheme 1
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Acknowledgements

The authors would like to express their gratitude to the following financial entities for funding this work: CSIR and NRF (South Africa), the European Union Erasmus Mundus scheme (EUROSA), and Senate Research and Postdoctoral (UWC). Authors also would like to thank Prof. Magda Monari of the University of Bologna for correcting the disorders in the crystal structures for us.

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Authors and Affiliations

  1. Department of Chemistry, University of the Western Cape, Private Bag X17, Bellville, 7535, South Africa

    Asanda V Busa & Martin Onani

  2. Department of Chemistry, Rutgers University – Newark, 73 Warren St, Newark, NJ, 07102-1811, USA

    Roger Lalancette

  3. Chemical Physics, Department of Chemistry, Lund University, Box 124, 221 00, Lund, Sweden

    Ebbe Nordlander

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  1. Asanda V Busa
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  2. Roger Lalancette
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Correspondence to Asanda V Busa.

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Busa, A.V., Lalancette, R., Nordlander, E. et al. New copper(II) salicylaldimine derivatives for mild oxidation of cyclohexane. J Chem Sci 130, 59 (2018). https://doi.org/10.1007/s12039-018-1455-y

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